This description addresses a process for the preparation of polyolefins from one or more olefinic monomers comprising combining under polymerization conditions said olefins with the product of combining i) an organometallic catalyst compound and ii) a cocatalyst complex comprising a trialkylsilyl-substituted carbenium cation and a suitable noncoordinating or weakly coordinating anion. These complexes exhibit good solubility in aliphatic solvents such that use in aliphatic solution based polymerization reaction processes can be conducted without the use of aromatic solvents or co-solvents and without the need for slurry means of introduction into chemical reaction environments. High number-average molecular weight polymers and copolymers at high rates of productivity were observed from the use of metallocene catalysts complexes when activated with [(3,5-Et3Si)2Ph)3C]+ [(C6F5) B]xe2x88x92 and used in a hexane-based solution polymerization.

This invention relates to the preparation of olefin polymers using catalyst systems based on ionic cocatalysts for organometallic or organometalloid catalyst complexes where the cocatalysts comprise carbenium-based cations and noncoordinating or weakly coordinating anions.
The term xe2x80x9cnoncoordinating anionxe2x80x9d is now accepted terminology in the field of olefin and vinyl monomer polymerization, both by coordination or insertion polymerization and carbocationic polymerization. See, for example, EP 0 277 003, EP 0 277 004, U.S. Pat. No. 5,198,401, U.S. Pat. No. 5,278,119, Baird, Michael C., et al, J. Am. Chem. Soc. 1994, 116, 6435-6436, U.S. Pat. No. 5,312,881, U.S. Pat. No. 5,502,017, U.S. Pat. No. 5,668,234, and WO 98/03558. The noncoordinating anions are described to function as electronic stabilizing cocatalysts, or counterions, for essentially cationic metallocene complexes which are active for polymerization. The term noncoordinating anion as used here applies both to truly noncoordinating anions and coordinating anions that are at most weakly coordinated to the cationic complex so as to be labile to replacement by olefinically or acetylenically unsaturated monomers at the insertion site. These noncoordinating anions can be effectively introduced into a polymerization medium, or premixed with an organometallic catalyst compound prior to introduction into the polymerization medium, as Bronsted acid salts containing charge-balancing countercations, ionic cocatalyst compounds. See also, the review articles by S. H. Strauss, xe2x80x9cThe Search for Larger and More Weakly Coordinating Anionsxe2x80x9d, Chem. Rev., 93, 927-942 (1993) and C. A. Reed, xe2x80x9cCarboranes: A New Class of Weakly Coordinating Anions for Strong Electrophiles, Oxidants and Superacidsxe2x80x9d, Acc. Chem. Res., 31, 133 -139 (1998).
Both of U.S. Pat. Nos. 5,198,401 and WO 97/35893 specifically address nitrogen-containing Bronsted acid cations capable of donating a proton, to suitable Lewis acidic organometallic catalyst compounds, as part of ionic cocatalyst compounds that in turn are capable of activating said organometallic compounds by rendering them cationic and providing a compatible, counterbalancing noncoordinating anion. U.S. Pat. No. 5,198,401 describes catalyst activator compounds represented by the formula [(Lxe2x80x2xe2x88x92H)+]d[(Mxe2x80x2)m+Q1Q2 . . . Qn]dxe2x88x92 where Lxe2x80x2 is a neutral base, H is a hydrogen atom and [(Mxe2x80x2)m+Q1Q2 . . . Qn] is a metal or metalloid atom subtended by a variety of ligands, preferably where M is boron and two or more of Qn are aromatic radicals, such as phenyl, napthyl and anthracenyl, each preferably fluorinated. Lxe2x80x2 is illustrated with various trialkyl-substituted ammonium complexes and N,N-dialkylanilinium complexes. WO 97/35893 describes cocatalyst activator compounds represented by the formula [L*xe2x88x92H]+[BQxe2x80x24]xe2x88x92 where L* includes nitrogen containing neutral Lewis bases, B is boron in an oxidation state of 3, and Qxe2x80x2 is a fluorinated C1-20 hydrocarbyl group, preferably a fluorinated aryl group. The cocatalyst compounds are said to be rendered soluble in aliphatic solvents by incorporation of olephilic groups, such as long chain alkyl or substituted-alkyl groups, into the Bronsted acid L*. Bis(hydrogenated-tallowalkyl)m ethyl ammonium and di(dicosyl)methyl-ammonium salts are exemplified.
EP 0 426 637 describes the use of the cocatalyst compound non-substituted triphenylcarbenium tetrakis(pentafluorophenyl)boronate as a proton-free ionizing agent that abstracts a metal ligand to form a catalytically active metallocene cation and a loosely coordinated anion. U.S. Pat. No. 5,502,017 addresses ionic metallocene catalysts for olefin polymerization comprising, as a cocatalyst component, a weakly coordinating anion comprising boron substituted with halogenated aryl substituents preferably containing silylalkyl substitution, such as para-silyl-t-butyldimethyl. This substitution is said to increase the solubility and thermal stability of the resulting metallocene salts. Examples 3-5 describe the synthesis and polymerization use of the cocatalyst compound triphenylcarbenium tetrakis (4-dimethyl-t-butylsilyl-2, 3, 5, 6-tetrafluorophenyl)borate.
Olefin solution polymerization processes are generally conducted in aliphatic solvents that serve both to maintain reaction medium temperature profiles and solvate the polymer products prepared. However, aryl-group containing activators, such as those having phenyl derivatives and other fused or pendant aryl-group substituents, are at best sparingly soluble in such solvents and typically are introduced in aryl solvents such as toluene. Solution polymerization processes in aliphatic solvents thus can be contaminated with toluene that must be removed to maintain process efficiencies and to accommodate health-related concerns for both industrial manufacturing processes and polymer products from them. Alternatively, relatively insoluble catalyst components can be introduced via slurry methods, but such methods required specialized handling and pumping procedures that complicate and add significant costs to industrial scale plant design and operation. Low solubility can also become disadvantageous should the process involve low temperature operation at some stage such as in typical adiabatic processes run in areas subject to low ambient temperatures. Additionally, separating or counteracting the build up in the recycle system of aromatic catalyst solvents may become another problem. At the same time means of maintaining high molecular weights in olefin polymers while operating at economically preferable high polymerization reaction temperatures and high polymer production rates is highly desirable. It is therefore desirable to identify olefin polymerization cocatalyst activators which are active for polymerization, particularly at elevated temperatures, which are more soluble in aliphatic solvents.
This invention addresses a process for the preparation of polyolefins from one or more olefinic monomers comprising combining under polymerization conditions said olefins with the reaction product of i) a transition metal organometallic catalyst compound and ii) a cocatalyst complex comprising a trialkylsilyl-substituted carbenium cation and a noncoordinating or weakly coordinating anion. The cocatalysts of the invention provide carbon compound by-products and weakly coordinating, stabilizing anions for essentially cationic transition metal organometallic catalyst complexes that exhibit high polymerization activities.
The invention provides a process for olefin polymerization in which anion-containing cocatalyst complexes and organometallic catalyst precursor compounds can be combined to form active catalysts for olefin polymerization. Subsequent contacting, or in situ catalyst formation essentially concurrent with said contacting, with insertion polymerizable monomers, those having accessible olefinic, acetylenic unsaturation, or with monomers having olefinic unsaturation capable of cationic polymerization. The catalyst according to the invention is suitable for preparing polymers and copolymers from olefinically and acetylenically unsaturated monomers.
The invention cocatalyst complexes can be represented by the following formula:
[((R1R2R3Si)5xe2x88x92nC6Hn)m(C6H5)3xe2x88x92mC]+[A]xe2x88x92,
where each of R1, R2, and R3 is independently a substituted or unsubstituted C1 to C32 hydrocarbyl group, n=1-4, m=1-3, and [A]xe2x88x92 is any noncoordinating or weakly coordinating anion suitable for use in olefin polymerization. Typically [A]xe2x88x92 is a halogenated, tetraryl-substituted Group 10-15 non-carbon, element-based anion, especially those that are have fluorine groups substituted for hydrogen atoms on the aryl groups, or on alkyl substituents on those aryl groups.
For illustration purposes trialkylsilyl group-substituted phenyl groups may be independently selected from the groups depicted below:
where any Rxe2x80x2 is independently any of the groups below except H and any Rxe2x80x2xe2x80x3 is independently any of the groups below:
The effective Group 8-15 element cocatalyst complexes of the invention are, in a preferable embodiment, derived from an ionic salt, comprising a 4-coordinate Group 10-14 element anionic complex, where Axe2x88x92 can be represented as:
[(M)Q1Q2 . . . Qi]xe2x88x92,
where M is one or more Group 10-15 metalloid or metal, preferably boron or aluminum, and either each Q is ligand effective for providing electronic or steric effects rendering [(Mxe2x80x2)Q1Q2 . . . Qn]xe2x88x92 suitable as a noncoordinating anion as that is understood in the art, or a sufficient number of Q are such that [(Mxe2x80x2)Q1Q2 . . . Qn]xe2x88x92 as a whole is an effective noncoordinating or weakly anion. Exemplary Q substituents specifically include fluorinated aryl groups, preferably perfluorinated aryl groups, and include substituted Q groups having substituents additional to the fluorine substitution, such as fluorinated hydrocarbyl groups. Preferred fluorinated aryl groups include phenyl, biphenyl, napthyl and derivatives thereof. The disclosures of U.S. Pat. Nos. 5,198,401, 5,296,433, 5,278,119, 5,447,895, 5,688,634, 5,895,771, WO 93/02099, WO 97/29845, WO 99/43717, WO 99/42467 and copending U.S. application Ser. No. 09/261,627, filed Mar. 3, 1999, and its equivalent WO 99/45042 are particularly instructive as to suitable Q substituents and are incorporated by reference for purposes of U.S. patent practice.
Additional suitable anions are known in the art and will be suitable for use with the metallocene catalysts of the invention. See U.S. Pat. No. 5,483,014, weakly coordinating anions from borane, carborane, borate, carborate, metalloborane, or metallocarborane complexes are described and exemplified. See also, the review articles by S. H. Strauss, xe2x80x9cThe Search for Larger and More Weakly Coordinating Anionsxe2x80x9d, Chem. Rev., 93, 927-942 (1993) and C. A. Red, xe2x80x9cCarboranes: A New Class of Weakly Coordinating Anions for Strong Electrophiles, Oxidants and Superacidsxe2x80x9d, Acc. Chem. Res., 31, 133-139 (1998).
In particular embodiments one Q group, or ligand, of the anionic complex may also be bonded to a metal/metalloid oxide support or polymeric support. See, for example, U.S. Pat. Nos. 5,427,991 and 5,939,347, each incorporated by reference for purposes of U.S. patent practice. Metal or metalloid oxide supports of the described bonding method for the invention include any metal/metalloid oxides, preferably those having surface hydroxyl groups exhibiting a pKa equal to or less than that observed for amorphous silica, i.e., pKa less than or equal to about 11. Accordingly any of the conventionally known silica support materials that retain hydroxyl groups after dehydration treatment methods will be suitable in accordance with the invention. Because of availability, both of silica and silica containing metal oxide based supports, for example, silica-alumina, are preferred. Silica particles, gels and glass beads are most typical.
Polymeric supports are preferably hydroxyl-functional-group-containing polymeric substrates, but functional groups may be any of the primary alkyl amines, secondary alkyl amines, and others, where the groups are structurally incorporated in a polymeric chain and capable of a acid-base reaction with the Lewis acid such that a ligand filling one coordination site of the Group 13 element is protonated and replaced by the polymer incorporated functionality. See, for example, the functional group containing polymers of U.S. Pat. No. 5,288,677, the functionalized polymers of U.S. Pat. Nos. 5,427,991 and the descriptions in copending applications U.S. Ser. No. 09/277,339, filed Mar. 26, 1999, and its equivalent PCT/99US/06135, and U.S. Ser. No. 09/092,752, filed Jun. 5, 1998, and its equivalent WO 98/55518. All are incorporated by reference for purposes of U.S. patent practice.
Other known methods for supporting catalyst systems comprising a noncoordinating anion cocatalyst will also be suitable as means for supporting the catalyst complexes of this invention. Thus the catalyst complexes of the invention may also physically deposited on or affixed to a suitable support material. See, for example, the teachings of WO 91/09882, WO 93/11172, WO 96/35726 and U.S. Pat. Nos. 4,463,135, and 5,610,115.
Transition metal compounds suitable as olefin polymerization catalysts by coordination or insertion polymerization in accordance with the invention will include the known organometallic transition metal compounds useful in traditional Ziegler-Natta coordination polymerization, particularly the metallocene compounds known to be useful in coordination polymerization, when such compounds are capable of catalytic activation by the cocatalyst activators described for the invention. These will typically include Group 3-10 transition metal compounds wherein at least one metal ligand can be abstracted by the cocatalyst activators, particularly those ligands including hydride, hydrocarbyl, and hydrocarbylsilyl, and lower alkyl-substituted (C1-C10) derivatives of those. Ligands capable of abstraction and transition metal compounds comprising them include those metallocenes described in the background art, see for example U.S. Pat. No. 5,198,401 and WO 92/00333. Syntheses of these compounds are well known from the published literature. Additionally, where the metal ligands include halogen, amido or alkoxy moieties (for example, biscyclopentadienyl zirconium dichloride) which are not capable of abstraction with the activating cocatalysts of the invention, they can be converted into suitable ligands via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See also EP-A1-0 570 982 for the reaction of organoaluminum compounds with dihalo-substituted metallocene compounds prior to addition of activating anion compounds. All documents are incorporated by reference for purposes of U.S. patent practice.
Additional description of metallocene compounds which comprise, or can be alkylated to comprise, at least one ligand capable of abstraction to form a catalytically active transition metal cation appear in the patent literature, e.g., EP-A-0 129 368, U. S. Pat. Nos. 4,871,705, 4,937,299, 5,324,800 EP-A-0 418 044, EP-A-0 591 756, WO-A-92/00333, WO-A-94/01471 and WO 97/22635. Such metallocene compounds can be described for this invention as mono- or biscyclopentadienyl substituted Group 3, 4, 5, or 6 transition metal compounds wherein the ancillary ligands may be themselves substituted with one or more groups and may be bridged to each other, or may be bridged through a heteroatom to the transition metal. The size and constituency of the ancillary ligands and bridging elements are not critical to the preparation of the ionic catalyst systems of the invention but should be selected in the literature described manner to enhance the polymerization activity and polymer characteristics being sought. Preferably the cyclopentadienyl rings (including substituted cyclopentadienyl-based fused ring systems, such as indenyl, fluorenyl, azulenyl, or substituted analogs of them), when bridged to each other, will be lower alkyl-substituted (C1-C6) in the 2 position (without or without a similar 4-position substituent in the fused ring systems) and may additionally comprise alkyl, cycloalkyl, aryl, alkylaryl and or arylalkyl substituents, the latter as linear, branched or cyclic structures including multi-ring structures, for example, those of U.S. Pat. Nos. 5,278,264 and 5,304,614. Such substituents should each have essentially hydrocarbyl characteristics and will typically contain up to 30 carbon atoms but may be heteroatom containing with 1-5 non-hydrogen/carbon atoms, e.g., N, S, O, P, Ge, B and Si. All documents are incorporated by reference for purposes of U.S. patent practice.
Metallocene compounds suitable for the preparation of linear polyethylene or ethylene-containing copolymers (where copolymer means comprising at least two different monomers) are essentially any of those known in the art, see again WO-A-92/00333 and U.S. Pat. Nos. 5,001,205, 5,198,401, 5,324,800, 5,304,614 and 5,308,816, for specific listings. Selection of metallocene compounds for use to make isotactic or syndiotactic polypropylene, and their syntheses, are well-known in the art, specific reference may be made to both patent literature and academic, see for example Journal of organometallic Chemistry 369, 359-370 (1989). Typically those catalysts are stereorigid asymmetric, chiral or bridged chiral metallocenes. See, for example, U.S. Pat. No. 4,892,851, U.S. Pat. No. 5,017,714, U.S. Pat. No. 5,296,434, U.S. Pat. No. 5,278,264, WO-A-(PCT/US92/10066) WO-A-93/19103, EP-A2-0 577 581, EP-A1-0 578 838, and academic literature xe2x80x9cThe Influence of Aromatic Substituents on the Polymerization Behavior of Bridged Zirconocene Catalystsxe2x80x9d, Spaleck, W., et al, Organometallics 1994, 13, 954-963, and xe2x80x9cansa-Zirconocene Polymerization Catalysts with Annelated Ring Ligands-Effects on Catalytic Activity and Polymer Chain Lengthsxe2x80x9d, Brinzinger, H., et al, Organometallics 1994, 13, 964-970, and documents referred to therein. Though many above are directed to catalyst systems with alumoxane activators, the analogous metallocene compounds will be useful with the cocatalyst activators of this invention for active coordination catalyst systems, when the halogen, amide or alkoxy containing ligands of the metals (where occurring) are replaced with ligands capable of abstraction, for example, via an alkylation reaction as described above, and another is a group into which the ethylene group xe2x80x94Cxe2x95x90Cxe2x80x94 may insert, for example, hydride, alkyl, or silyl. See additional description in G. G. Hlatky, xe2x80x9cMetallocene catalysts for olefin polymerization Annual review of 1996xe2x80x9d, Coordination Chemistry Reviews, 181, 243-296 (Elsevier Science, 1999). All documents are incorporated by reference for purposes of U.S. patent practice.
Representative metallocene compounds can have the formula:
LALBLCiMDE
where, LA is a substituted cyclopentadienyl or heterocyclopentadienyt ancillary ligand xcfx80-bonded to M; LB is a member of the class of ancillary ligands defined for LA, or is J, a heteroatom ancillary ligand "sgr"-bonded to M; the LA and LB ligands may be covalently bridged together through one or more Group 13-16 element-containing linking groups; LCi is an optional neutral, non-oxidizing ligand having a dative bond to M (i equals 0 to 3); M is a Group 4 or 5 transition metal; and, D and E are independently monoanionic labile ligands, each having a "sgr"-bond to M, optionally bridged to each other or LA or LB, which can be broken for abstraction purposes by a suitable activator and into which a polymerizable monomer or macromonomer can insert for coordination polymerization. Also, the use of hetero-atom containing rings or fused rings, where a non-carbon Group 13, 14, 15 or 16 atom replaces one of the ring carbons is considered for this specification to be within the terms xe2x80x9ccyclopentadienylxe2x80x9d, xe2x80x9cindenylxe2x80x9d, and xe2x80x9cfluorenylxe2x80x9d. See, for example, the background and teachings of WO 98/37106, having common priority with U.S. Ser. No. 08/999,214, filed Dec. 29, 1997, and WO 98/41530, having common priority with U.S. Ser. No. 09/042,378, filed Mar. 13, 1998, both incorporated by reference for purposes of U.S. patent practice.
Non-limiting representative metallocene compounds include mono-cyclopentadienyl compounds such as pentamethylcyclopentadienyltitanium isopropoxide, pentamethylcyclopentadienyltribenzyl titanium, dimethylsilyltetramethyl-cyclopentadienyl-tert-butylamido titanium dichloride, pentamethylcyclopentadienyl titanium trimethyl, dimethylsilyltetramethyl-cyclopentadienyl-tert-butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dihydride, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dimethyl, unbridged biscyclopentadienyl compounds such as bis(1,3-butyl, methylcyclopentadienyl) zirconium dimethyl, pentamethylcyclopentadienyl-cyclopentadienyl zirconium dimethyl, (tetramethylcyclopentadienyl)(n-propyl-cyclopentadienyl)zirconium dimethyl; bridged bis-cyclopentadienyl compounds such as dimethylsilylbis(tetrahydroindenyl) zirconium dichloride and silacyclobutyl(tetramethylcyclopentadienyl)(n-propyl-cyclopentadienyl) zirconium dimethyl; bridged bis-indenyl compounds such as dimethylsily-bisindenyl zirconium dichloride, dimethylsily-bisindenyl hafnium dimethyl, dimethylsilylbis(2-methylbenzindenyl) zirconium dichloride, dimethylsilylbis(2-methylbenzindenyl) zirconium dimethyl; and fluorenyl ligand-containing compounds, e.g., diphenylmethyl(fluorenyl)(cyclopentadienyl)zirconium dimethyl; and the additional mono- and biscyclopentadienyl compounds such as those listed and described in U.S. Pat. Nos. 5,017,714, 5,324,800, WO 92/00333 and EP-A-0 591 756. All documents are incorporated by reference for purposes of U.S. patent practice.
Representative traditional Ziegler-Natta transition metal compounds include tetrabenzyl zirconium, tetra bis(trimethylsilylmethyl) zirconium, oxotris(trimethlsilylmethyl) vanadium, tetrabenzyl hafnium, tetrabenzyl titanium, bis(hexamethyl disilazido)dimethyl titanium, tris(trimethyl silyl methyl) niobium dichloride, tris(trimethylsilylmethyl) tantalum dichloride. The important features of such compositions for coordination polymerization are the ligand capable of abstraction and that ligand into which the ethylene (olefinic) group can be inserted. These features enable the ligand abstraction from the transition metal compound and the concomitant formation of the ionic catalyst composition of the invention.
Additional organometallic transition metal compounds suitable as olefin polymerization catalysts in accordance with the invention will be any of those Group 3-11 that can be converted by ligand abstraction into a catalytically active cation and stabilized in that active electronic state by a noncoordinating or weakly coordinating anion sufficiently labile to be displaced by an olefinically unsaturated monomer such as ethylene.
Exemplary compounds include those described in the patent literature. International Patent Publications WO 96/23010, WO 97/48735 and Gibson, et. al., Chem. Comm., pp. 849-850 (1998) disclose diimine-based ligands for Group 8-10 metal compounds shown to be suitable for ionic activation and olefin polymerization. See also WO 97/48735. Transition metal polymerization catalyst systems from Group 5-10 metals wherein the active transition metal center is in a high oxidation state and stabilized by low coordination number polyanionic ancillary ligand systems are described in U.S. Pat. No. 5,502,124 and its divisional U.S. Pat. No. 5,504,049. See also the (Group 5 organometallic catalyst compounds of U.S. Pat. No. 5,851,945 and the tridentate ligand containing Group 5-10 organometallic catalyst compounds of copending U.S. application Ser. No. 09/302243, filed Apr. 29, 1999, and its equivalent PCT/US99/09306. Group 11catalyst precursor compounds, capable of activation with ionizing cocatalysts, useful for olefins and vinyl group-containing polar monomers are described and exemplified in WO 99/30822 and/its priority document, including U.S. Pat. No. application Ser. No. 08/991,160 filed Dec. 16, 1997. Each of these documents is incorporated by reference for the purposes of U.S. patent practice.
U.S. Pat. No. 5,318,935 describes bridged and unbridged bisamido transition metal catalyst compounds of Group 4 metals capable of insertion polymerization of (-olefins. Bridged bis(arylamido) Group 4 compounds for olefin polymerization are described by D. H. McConville, et al, in Organometallics 1995, 14, 5478-5480. Synthesis methods and compound characterization are presented. Further work appearing in D. H. McConville, et al, Macromolecules 1996, 29, 5241-5243, described bridged bis(arylamido) Group 4 compounds that are active catalysts for polymerization of 1-hexene. Additional transition metal compounds suitable in accordance with the invention include those described in WO 96/40805. Cationic Group 3 or Lanthanide metal complexes for coordination polymerization of olefins is disclosed in copending U.S. application Serial number 09/408050, filed Sep. 29, 1999, and its equivalent PCT/US99/22690. The precursor metal compounds are stabilized by a monoanionic bidentate ancillary ligand and two monoanionic ligands and are capable of activation with the ionic cocatalysts of the invention. Each of these documents is incorporated by reference for the purposes of U.S. patent practice.
Additional description of suitable organometallic or organometalloid catalyst precursor compounds may be found in the literature, any of such will be suitable where comprising, or where capable of alkylation to comprise, ligands capable of ionizing abstraction. See, for instance, V. C. Gibson, et al, xe2x80x9cThe Search for New-Generation Olefin Polymerization Catalysts: Life Beyond Metallocenesxe2x80x9d, Angew. Chem Int. Ed, 38, 428-44 (1999).
When using the above catalysts of the invention, the total catalyst system will generally additionally comprise one or more organometallic compound. Such compounds as used in this application and its claims is meant to include those compounds effective for removing polar impurities from the reaction environment and for increasing catalyst activity. Impurities can be inadvertently introduced with any of the polymerization reaction components, particularly with solvent, monomer and catalyst feed, and adversely affect catalyst activity and stability. It can result in decreasing or even elimination of catalytic activity, particularly when ionizing anion pre-cursors activate the catalyst system. The polar impurities, or catalyst poisons include water, oxygen, metal impurities, etc. Preferably steps are taken before provision of such into the reaction vessel, for example by chemical treatment or careful separation techniques after or during the synthesis or preparation of the various components, but some minor amounts of organometallic compound will still normally be used in the polymerization process itself
Typically these compounds will be organometallic compounds such as the Group-13 organometallic compounds of U.S. Pat. Nos. 5,153,157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132 and that of WO 95/07941.
Exemplary compounds include triethyl aluminum, triethyl borane, triisobutyl aluminum, methylalumoxane, and isobutyl aluminumoxane. Those compounds having bulky or C6-C20 linear hydrocarbyl substituents covalently bound to the metal or metalloid center being preferred to minimize adverse interaction with the active catalyst. Examples include triethylaluminum, but more preferably, bulky compounds such as triisobutylaluminum, triisoprenylaluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n-octylaluminum, or tri-n-dodecylaluminum. When alumoxane is used as activator, any excess over the amount needed to activate tile catalysts present can act as a poison scavenger compound and additional organometallic compounds may not be necessary. Alumoxanes also may be used in scavenging amounts with other means of activation, e.g., methylalumoxane and triisobutyl-aluminoxane with boron-based activators. The amount of such compounds to be used with catalyst compounds of the inventions is minimized during polymerization reactions to that amount effective to enhance activity (and with that amount necessary for activation of the catalyst compounds if used in a dual role) since excess amounts may act as catalyst poisons.
The catalyst complexes of the invention useful in polymerization of unsaturated monomers conventionally know to be polymerizable under coordination polymerization using metallocenes. Such conditions are well known and include solution polymerization, slurry polymerization, gas-phase polymerization, and high-pressure polymerization The catalyst of the invention may be supported (preferably as described above) and as such will be particularly useful in the known operating modes employing fixed-bed, moving-bed, fluid-bed, slurry or solution processes conducted in single, series or parallel reactors. Pre-polymerization of supported catalyst of the invention may also be used for further control of polymer particle morphology in typical slurry or gas phase reaction processes in accordance with conventional teachings.
In alternative embodiments of olefin polymerization methods for this invention, the catalyst system is employed in liquid phase (solution, slurry, suspension, bulk phase or combinations thereof), in high-pressure liquid or supercritical fluid phase, or in gas phase. Each of these processes may also be employed in singular, parallel or series reactors. The liquid processes comprise contacting olefin monomers with the above described catalyst system in a suitable diluent or solvent and allowing said monomers to react for a sufficient time to produce the invention copolymers. Hydrocarbyl solvents are suitable, both aliphatic and aromatic, hexane is preferred. BuIk and slurry processes are typically done by contacting the catalysts with a slurry of liquid monomer, the catalyst system being supported. Gas phase processes typically use a supported catalyst and are conducted in any manner known to be suitable for ethylene homopolymers or copolymers prepared by coordination polymerization. Illustrative examples may be found in U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,382,638, 5352,749, 5,408,017, 5,436,304, 5,453,471, and 5,463,999, 5,767,208 and WO 95107942. Each is incorporated by reference for purposes of U.S. patent practice.
Generally speaking the polymerization reaction temperature can vary from about 40xc2x0 C. to about 250xc2x0 C. Preferably the polymerization reaction temperature will be from 60xc2x0 C. to 220xc2x0. The pressure can vary from about 1 mm Hg to 2500 bar, preferably from 0.1 bar to 1600 bar, most preferably from 1.0 to 500 bar.
For homogenous solution polymerization best results may be obtained when the quantity and type of solvent used to introduce the catalyst is controlled as well as the manner of introduction. Generally it is believed preferable to achieve full solution and avoid slurried systems, and hence fairly high concentrations of the catalyst, at low temperatures and use low solvent amounts. The ease with which these objectives can be achieved may vary with the solubility of the non-coordinating anion and transition metal components. Some of the more active catalysts or those likely to give a higher mol weight at a given temperature, may have reduced solubility or may be modified for increased solubility.
The invention is hence especially suitable for use with solution polymerization using bridged fluorenyl systems and/or naphthyl containing non-coordinating anions optimized for higher temperature and/or higher molecular weight production at temperature in excess of 130 or even 170 degrees C and up to 250 degrees C.
Linear polyethylene, including high and ultra-high molecular weight polyethylenes, including both homo- and copolymers with other alpha-olefin monomers, alpha-olefinic and/or non-conjugated diolefins, for example, C3-C20 olefins, diolefins or cyclic olefins, are produced by adding ethylene, and optionally one or more of the other monomers, to a reaction vessel under low pressure (typically  less than 50 bar), at a typical temperature of 40-250xc2x0 C. with the invention catalyst that has been slurried with a solvent, such as hexane or toluene. Heat of polymerization is typically by cooling. Gas phase polymerization can be conducted, for example, in a continuous fluid bed gas-phase reactor operated at 2000-3000 kPa and 60-160xc2x0 C., using hydrogen as a reaction modifier (100-200 PPM), C4-C8 comonomer feedstream (0.5-1.2 mol %), and C2 feedstream (25-35 mol %). See, U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670 and 5,405,922 and 5,462,999, which are incorporated by reference for purposes of U.S. patent practice.
Ethylene-xcex1-olefin (including ethylene-cyclic olefin and ethylene-xcex1-olefin-diolefin) elastomers of high molecular weight and low crystallinity can be prepared utilizing the catalysts of the invention under traditional solution polymerization processes or by introducing ethylene gas into a slurry utilizing the xcex1-olefin or cyclic olefin or mixture thereof with other monomers, polymerizable and not, as a polymerization diluent in which the invention catalyst is suspended. Typical ethylene pressures will be between 10and 1000 psig (69-6895 kPa) and the polymerization diluent temperature will typically be between 40 and 160xc2x0 C. The process can be carried out in a stirred tank reactor, or more than one operated in series or parallel: See the general disclosure of U.S. Pat. No. 5,001,205 for general process conditions. See also, International Applications WO 96/33227 and WO 97/22639. All documents are incorporated by reference for description of polymerization processes, metallocene selection and useful scavenging compounds.
Other olefinically unsaturated monomers besides those specifically described above may be polymerized using the catalysts according to the invention, for example, styrene, alkyl-substituted styrenes, isobutylene and other geminally disubstituted olefins, ethylidene norbornene, norbornadiene, dicyclopentadiene, and other olefinically-unsaturated monomers, including other cyclic olefins, such as cyclopentene, norbornene, alkyl-substituted norbornenes, and vinyl group-containing polar monomers capable of coordination polymerization. See, for example, U.S. Pat. Nos. 5,635,573, 5,763,556, and WO 99/30822. Additionally, alpha-olefinic macromonomers of up to 1000 mer units, or more, may also be incorporated by copolymerization yielding branch-containing olefin polymers. Additionally oligomerization, dimerization, hydrogenation, olefin/carbon monoxide copolymerization, hydroformulation, hydrosilation, hydroamination and related catalytic reactions employing organometallic cationic complexes can be accomplished using the cocatalyst complexes of the invention with selected organometallic compounds as known in the art.
The catalyst compositions of the invention can be used as described above individually for coordination polymerization or can be mixed to prepare polymer blends with other known olefin polymerization catalyst compounds. By selection of monomers, blends of coordination catalyst compounds, polymer blends can be prepared under polymerization conditions analogous to those using individual catalyst compositions. Polymers having increased MWD for improved processing and other traditional benefits available from polymers made with mixed catalyst systems can thus be achieved.
The formation of blended polymers can be achieved ex situ through mechanical blending or in situ through the use of a mixed catalyst system. It is generally believed that in situ blending provides a more homogeneous product and allows the blend to be produced in one step. The use of mixed catalyst systems for in situ blending involves combining more than one catalyst in the same reactor to simultaneously produce multiple distinct polymer products. This method requires additional catalyst synthesis and the various catalyst components must be matched for their activities, the polymer products they generate at specific conditions, and their response to changes in polymerization conditions.
The following examples are presented to illustrate the foregoing discussion. All parts, proportions and percentages are by weight unless otherwise indicated. All examples were carried out in dry, oxygen-free environments and solvents. Although the examples may be directed to certain embodiments of the present invention, they are not to be viewed as limiting the invention in any specific respect. In these examples certain abbreviations are used to facilitate the description. These include standard chemical abbreviations for the elements and certain commonly accepted abbreviations, such as: Me=methyl, Et=ethyl, t-Bu=tertiary-butyl, Cp=cyclopentadienyl, Ind=idenyl, Flu=fluorenyl, THF (or thf)=tetrahydrofuran, Ph=phenyl, and pfp=pentafluorophenyl.
All molecular weights are weight average molecular weight unless otherwise noted. Molecular weights (weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by Gel Permeation Chromatography, unless otherwise noted, using a Waters 150 Gel Permeation Chromatograph equipped with a differential refractive index (DRI) and low angle light scattering (LS) detectors and calibrated using polystyrene standards. Samples were run in 1,2,4-trichlorobenzene (135xc2x0 C.) using three Polymer Laboratories PC Gel mixed B columns in series. This general technique is discussed in xe2x80x9cLiquid Chromatography of Polymers and Related Materials IIIxe2x80x9d J. Cazes Ed., Marcel Decker, 1981, page 207, which is incorporated by reference for purposes of U.S. Pat. No. practice herein. No corrections for column spreading were employed; however, data on generally accepted standards, e.g. National Bureau of Standards Polyethylene 1475, demonstrated a precision with 0.2 units for Mw/Mn which was calculated from elution times.

Carbenium cationic complexes suitable for polymerization catalysts


The present invention relates to a method for producing a flat article comprising a material that contains the products of several reactions. The method comprises the following steps: carrying out a pre-cross-linking of a mixture comprising an epoxydation product of a carboxylic acid ester using at least one cross-linking agent in order to form a moldable material; molding the moldable material in the shape of a flat article; and curing the molded material in order to produce a flat article, wherein the pre-cross-linking reaction is separate from the curing reaction. This invention also relates to a moldable material that can be stored and to a flat article that can be obtained from the same.

The present invention relates to a method for producing a flat article comprising a material that contains polyreaction products. The method comprises the following steps: carrying out pre-crosslinking of a mixture comprising an epoxidation product of at least one carboxylic acid ester using at least one crosslinking agent to form a moldable material; molding the moldable material in the shape of a flat article; and curing the molded material to produce a flat article, wherein the pre-crosslinking reaction is separate from the curing reaction. The invention further relates to a moldable material that can be stored and to a flat article that can be obtained therefrom.
Linoleum has long been known as a resilient floor covering based on renewable raw materials. Because of its natural constituents, linoleum has achieved great importance based on its biological suitability for use in construction as well as environmental considerations. However, in the production of linoleum coverings the last step of the process requires a heat treatment, the so-called xe2x80x9cripening time,xe2x80x9d that lasts several weeks. Although measures have been undertaken in the prior art to shorten this ripening time and thus achieve higher productivity, continuous methods for producing linoleum flooring are thus far unknown in the art.
For this reason flat articles, based on renewable raw materials, that are composed of other materials have been described in the prior art. German Patent 22 41 535, for example, describes a coating material for flat textile articles based on epoxidation products of esters of unsaturated fatty acids and polyvalent aliphatic alcohols.
However, the epoxidized oils and fatty acids used in such a method are liquid in the unprocessed state, with the result that flat articles cannot be molded from said substances in the raw state. Thus, in the production of flat articles from such a material it is common to carry out pre-crosslinking of the oils and/or fatty acids to give a highly viscous, moldable intermediate product (prepolymer). After molding into flat articles, a second crosslinking step is then carried out to give a usable material (final crosslinking). Termination of the first crosslinking step is problematic. In principle, a two-step reaction can be carried out in the following manner:
(I) Pre-crosslinking in which one of the crosslinking components is present in deficit (epoxidation product or crosslinking agent). Full crosslinking is carried out with addition of the component present in deficit.
(II) Different temperatures in the individual process steps.
(III) Use of separate crosslinking agents having different reactivities.
(IV) Different mechanisms in both process steps.
International Patent WO 90/107607 describes a method in xe2x80x9ctwo reaction phases,xe2x80x9d whereby in the first reaction phase a mixture of a stand oil with fillers is homogenized, then partially polymerized and partially crosslinked at elevated temperatures, using a peroxide, to give an intermediate product. The powdered intermediate product is then homogenized with an elastomeric natural or synthetic material, fillers, and a peroxide, and is again crosslinked and polymerized at elevated temperature.
Coating materials that are based on renewable raw materials and used for coating flat textile articles or release paper are known from German Patent Application 41 35 664. The coating materials are composed of a combination of epoxidation products of esters of unsaturated fatty acids and partial esters of polycarboxylic acids with polyether polyols in addition to a hydrophobing agent. These coating materials are used for the production of floor coverings. It is disadvantageous, however, that the top layer of coverings produced in this way is very rough and non-transparent. Furthermore, the surface of these coverings is not sufficiently soil-repellent and exhibits poor through-hardening.
Spreadable coating materials for the production of flat articles based on renewable raw materials are known from International Patent WO 96/15203. However, due to the use of so-called xe2x80x9ccoating pastesxe2x80x9d contained in the coating materials, the production of said flat articles is limited to coating methods.
International Patent WO 98/28356 describes a method for producing flat articles based on renewable raw materials, in which flat articles with satisfactory material properties can be obtained by pressing, calendering, or extruding. An intermediate product that can be stored (prepolymer) is obtained, however, only if either the crosslinking agent or the epoxidation product is present in deficit. The prepolymer is converted to the fully crosslinked material in the second crosslinking step by addition of the component that is present in deficit. This method has the disadvantage that a considerable portion of the component first added in deficit must be compounded into the already viscous, pre-crosslinked material.
Since the reactions underlying pre-crosslinking and final crosslinking in the prior art are always based on the same reaction mechanism, it is difficult to obtain a further processable, storable intermediate product by timely termination of pre-crosslinking or by use of a component in deficit.
The object of the present invention, therefore, is to provide a novel method for producing a flat article from renewable raw materials in which essentially no ripening time is necessary and in which the rate of pre-crosslinking can be better regulated. A further object is that the pre-crosslinked intermediate product has a practically unlimited storage life.
This object is achieved by the embodiments characterized in the claims.
In particular, a method for producing a flat article comprising a
material that contains polyreaction products is provided which comprises the following steps:
(1) Compouding of an epoxidation product of at least one carboxylic acid ester using at least one crosslinking agent,
(2) Pre-crosslinking or partial crosslinking of the mixture obtained in step (1) to form a moldable material,
(3) Molding of the moldable material obtained in step (2) in the shape of a flat article, and
(4) Curing, further crosslinking, or final crosslinking of the molded material to produce the flat article,
wherein the pre-crosslinking reaction in step (2) is separate from the curing reaction in step (4).
The present invention is based on the knowledge that the disadvantages of known methods of the prior art can be avoided by having separate chemical reactions or chemical reaction mechanisms for pre-crosslinking and for curing. To this end, at least two different reactions I and II occur in the mixture obtained by compounding (1), for example by the presence of at least two crosslinkable groups A and B. For pre-crosslinking in step (2), essentially only one reaction I proceeds, for example by reaction of only one crosslinkable group A, that is, a class of similar crosslinkable groups. Reaction II, which is different from reaction I, does not proceed significantly under the reaction conditions for pre-crosslinking. For example, group B, which is different from A, is essentially stable or inert under the reaction conditions for pre-crosslinking, and in this step is practically unreacted. Reaction I, for example, halts after the consumptionxe2x80x94that is, the essentially complete reactionxe2x80x94of group A to produce the moldable material. Furthermore, a suitable agent can be used to terminate reaction I after a desired reaction rate is achieved to produce the moldable material.
According to the invention, the second crosslinking step, that is, reaction IIxe2x80x94the reaction of group B, for examplexe2x80x94is initiated or started only by modification of the reaction conditions. In the context of the present invention, xe2x80x9cmodification of the reaction conditionsxe2x80x9d means an elevation in temperature or an increase or decrease in pressure, addition of reaction-initiating agents such as radical-forming initiators, and/or exposure of the mixture obtained in step (1) or the partially crosslinked material obtained by pre-crosslinking (2) to radiation, such as UV, electron beam, or IR radiation.
For example, pre-crosslinking (2) can be carried out at a relatively low temperature T1, optionally with radiation, at which reaction I proceeds, and group A, for example, is at least partially reacted, for example by esterification or etherification or a condensation, substitution, or addition reaction, optionally associated with a ring opening. At this temperature T1, reaction II does not proceed to a significant extent, and there is practically no conversion of group B, for example. For final crosslinking, at a specified time the moldable material can be heated to a higher temperature T2 at which reaction II, for example a radical crosslinking of group B, is initiated, such as by decomposition of a heat-sensitive group B itself or by a radical initiator that decomposes only at a temperature T2. In addition, the mixture obtained in step (1) during pre-crosslinking (2) can be exposed to radiation, for example UV radiation, which has brought about reaction I, for example crosslinking of group A. In contrast, crosslinking of group B is initiated only by an increase in temperature or another type of radiation such as IR or electron beam radiation or UV radiation at another wavelength, during final crosslinking (4). Also, the addition of, for example, radical- or ion-forming initiators or exposure to an atmosphere containing a reactive gas such as oxygen can be understood as modification of the reaction conditions according to the invention.
A major advantage of the present invention, therefore, is that in
a preferred embodiment the pre-crosslinking automatically terminates after reaction of the first crosslinkable groups is complete, and as a rule, appreciable crosslinking by the second crosslinkable groups beyond a moldable product does not occur in this step.
The epoxidation product of at least one carboxylic acid ester is preferably the epoxidation product of one or several esters of unsaturated fatty acids, preferably an epoxidized natural triglyceride or a derivative thereof. Epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, epoxidized rapeseed oil, or vernonia oil or a mixture containing at least two of these epoxidation products can be used, for example. In one embodiment these epoxidation products are only partially epoxidized; that is, in addition to epoxidized double bonds there remain unreacted double bonds in the carboxylic acid ester. The alcohol component of these carboxylic acid esters is not subject to any particular limitation. Dipropylene glycol, propanediols, butanediols, hexanediols, hexanetriols, glycerin, or pentaerythritol are examples of alcohol components that can be used. The carboxylic acid component is not subject to any particular limitation.
According to the present invention, the mixture obtained in step (1) is crosslinked in two crosslinking steps (2) and (4). In the first crosslinking step (2) a moldable intermediate product that can be stored is produced from liquid raw materials, for example. This crosslinking step (2) can be carried out after the compounding step (1) as well as simultaneously with the compounding step (1). After molding (3) in the shape of a flat article, the intermediate product acquires its final functional properties through curing and the second crosslinking step (4).
Furthermore, according to the invention the pre-crosslinking reaction is separate from the curing reaction. For example, when partially epoxidized carboxylic acid esters of unsaturated fatty acids are used in a first crosslinking step, the epoxy groups are preferably completely reacted, and in a second crosslinking step the remaining unsaturated double bonds
are crosslinked by radical polymerization, for example. In particular, the second crosslinking step can be carried out using essentially completely epoxidized carboxylic acid esters via radical hydrogen abstraction of the pre-crosslinked material, and recombination.
Reaction of the epoxy groups preferably is carried out with at least bifunctional compounds, so-called xe2x80x9ccrosslinking agents,xe2x80x9d for example by nucleophilic attack and addition to the epoxy group.
According to the present invention, the term xe2x80x9ccrosslinkingxe2x80x9d encompasses an increase in molar mass or molecular size. For example, the term xe2x80x9ccrosslinkingxe2x80x9d is associated with an increase in viscosity of the moldable material in comparison to the mixture obtained in step (1).
According to one embodiment of the present invention, so-called xe2x80x9cacid crosslinking agents,xe2x80x9d that is, di- or polycarboxylic acids or derivatives thereof, are used as reactants in such a reaction. In one embodiment, such di- or polycarboxylic acids or derivatives thereof contain at least one double bond per molecule. Maleic acid, itaconic acid, fumaric acid, succinic acid, methylsuccinic acid, malic acid, phthalic acid, tartaric acid, citraconic acid, furandicarboxylic acid, or a mixture of at least two of said acids are preferably used as dicarboxylic acids. Acids containing three or more carboxylic acid groups, such as citric acid, aconitic acid, and trimellitic acid, are preferably used as polycarboxylic acids.
Anhydrides or partial esters or derivatives having at least one free carboxylic acid group can be used as derivatives of di- or polycarboxylic acids. The alcohol component of the partial esters is not subject to any particular limitation; however, polyols such as dipropylene glycol, propanediols, butanediols, hexanediols, hexanetriols, glycerin, or pentaerythritol are preferably used as the alcohol component.
In one embodiment, a mixture of a partial ester of maleic acid anhydride and dipropylene glycol together with citric acid as crosslinking agent is used, where the amount of citric acid is less than or equal to 50 wt %, preferably less than or equal to 25 wt %, relative to the total quantity of crosslinking agent.
Moreover, the crosslinkable groups required for curing (4) may be introduced via the crosslinking agent.
The reaction of the epoxidation product with the crosslinking agent is preferably induced thermally and/or by radiation. In the case of thermal induction, the reaction is carried out, for example, at a temperature ranging from room temperature to 280xc2x0 C., preferably from room temperature to 200xc2x0 C., in particular to a temperature of 150xc2x0 C. UV radiation, electron beam radiation, and/or IR radiation may be used as the reaction-inducing radiation.
A reaction induced by UV radiation should be carried out in the presence of at least one UV initiator, and with electron beam radiation the addition of at least one UV initiator may be omitted. The UV initiators that may be used according to the invention can be radical or cationic UV initiators or a mixture of these types of UV initiators. Preferred examples of radical UV initiators include benzophenone, benzophenone derivatives, phosphine oxides, xcex1-morpholinoketones, quinone, quinone derivatives, xcex1-hydroxyketones, or mixtures thereof. Preferred examples of cationic UV initiators include triarylsulfonium salts, which can be present as one type or as a mixture of different triarylsulfonium salts, or diaryliodonium salts or mixtures thereof. The UV initiators are present, for example, in quantities of less than or equal to 15 wt %, preferably 0.05 to 8 wt %, relative to the quantity of the material containing polyreaction products.
In one embodiment according to the invention, in addition to the UV initiator at least one photosensitizer, such as a compound based on anthracene, perylene, or thioxanthene-9-one, is present which
activates the UV initiator and which can intensify the effect thereof. The concentration of the UV initiator can thus be reduced. UV radiation used according to the invention lies in a generally common range, that is, between 200 nm and 380 nm. IR radiation used according to the invention lies in a generally common range, for example between 760 nm and 0.5 mm.
The material containing polyreaction products preferably comprises 10 to 99 wt % binders relative to the total quantity of the material containing polyreaction products. The term xe2x80x9cbinderxe2x80x9d encompasses the crosslinking monomer and prepolymer components as well as crosslinking agents. In the mixture obtained in step (1), the respective weight quantities of the crosslinking agent and the epoxidation product are preferably 5 to 80 wt %, relative to the total quantity of the material containing polyreaction products.
Furthermore, in compounding step (1) additional additives or components, such as fillers, titanium dioxide, pigments for embossing, hydrophobing agents, auxiliary agents, and possibly co-crosslinking agents such as triallylisocyanurate, triallylcyanurate, ethylene glycol dimethacrylate, trimethylolpropane-trimethacrylate, and m-phenylene-bis-maleinimide may be admixed. The fillers are preferably wood dust, chalk, cork powder, barium sulfate, silicic acid, kaolin, quartz-kaolinite mixture, talc, glass, textile fibers, glass fibers, plant fibers, cellulose fibers, or polyester fibers, and nanoscale xe2x80x9cintelligentxe2x80x9d fillers such as organically modified bentonites. Examples of auxiliary agents that may be used include tall oils, synthetic or natural resins such as balsamic resins, copal resins, or hydrocarbon resins, and/or desiccants such as compounds of the metals Al, Li, Ca, Ba, Fe, Mg, Mn, Pb, Zn, Zr, Ce, Sn, or Co, or a combination containing at least two of these compounds.
As a result of pre-crosslinking (2) of the partially liquid components, the intermediate product formed has a specific pre-crosslinking rate and quasi-thermoplastic properties and is therefore moldable. Since reaction I,
for example the reaction of the first crosslinkable groups A, proceeds essentially to completion and curing according to the invention can be performed only by modifying the reaction conditions by initiating reaction II, for example by crosslinking of second crosslinkable groups B, the moldable intermediate product surprisingly has a practically unlimited storage life. The partially cured material can be comminuted (granulated or powdered) after the pre-crosslinking step (2), and can be stored in powdered form, for example.
The term xe2x80x9cmoldable materialxe2x80x9d applied to an intermediate product in this context means an essentially liquid reaction product as well as a highly viscous reaction product as binder. According to the present invention, the crosslinking rate of the pre-crosslinked moldable material obtained in step (2) is less than the crosslinking rate of the material containing polyreaction products in the form of a flat article obtained after curing (4).
The crosslinking rate of the moldable material can be controlled by the ratio of the number of first crosslinkable groups to the number of second crosslinkable groups, without significantly influencing the overall number of crosslinking groups and thus the crosslinking rate of the end product. If the relative number of first crosslinkable groups is relatively small, a rather low-viscosity moldable material is obtained as the intermediate product. If the relative number of first crosslinkable groups is larger, an intermediate product with a more solid consistency is obtained which can be processed as a granulate or powder, for example. In the case of epoxidation products of carboxylic acid esters of unsaturated fatty acids, the ratio of epoxy groups to unsaturated double bonds can be controlled, for example, by the epoxidation rate or via hydrogen abstraction by the peroxide dosage during crosslinking.
In addition, the consistency of the moldable material obtained in step (2) is influenced by whether a bifunctional or trifunctional crosslinking agent, for example, is used. Of course, the consistency also depends on the type and quantity
of additional components compounded, such as fillers, for example.
An advantage of the method according to the invention, therefore, is that the moldable pre-crosslinked material obtained in step (2) can be processed into a flat article using common methods such as pressing, calendering, or extruding.
Molding (3) of the compounded material can be carried out before curing (4) or simultaneously with curing (4). The pre-crosslinked material can be shaped in customary processing machines such as presses, double band presses, calenders, adaptive universal multiple access (AUMA) facilities, or thermoset machines, or by extruders with slot dies. for example. In addition, for embossing, differently colored chips or granules of an otherwise practically identical material can be interspersed in the material web obtained, whereupon the web can be given its final shape in a calender, AUMA facility, or thermoset machine, etc., for example.
Furthermore, an embossing method can be used in which, before curing (4), a patterned or printed absorbent material is applied to the material molded as a flat article. To avoid stresses in the flat article, material of the same type, which optionally is printed, may optionally be applied to the reverse side as a countermeasure. The absorbent material is preferably a cellulose non-woven fabric made of reclaimed cellulose fibers having a high specific surface, for example, which is characterized by high absorptivity, high dry and wet strengths, and low shrinkage. The weight per unit area of such cellulose non-woven fabrics ranges from 25 to 50 g/m2, for example. During subsequent pressing, a portion of the not yet fully crosslinked binder according to the invention penetrates the absorbent material and forms a thin top layer or wear layer after curing, which optionally can be lacquered by customary methods on the top side of the flat article embossed in such a manner. The top layer or wear layer of the patterned or printed material is thereby protected from abrasion.
One advantage of such a one-step embossing method is that a flat article constructed from the material defined above may be imprinted as desired, which for flat articles made of linoleum, for example, is not applicable.
According to the present invention, the intermediate product can be further crosslinked and cured in a second crosslinking step, either after or simultaneously with molding. Curing (4) may be performed by common methods such as pressing, for example by using a jaw press, AUMA facility, double band press, or calendering method, by simple passage through a heated channel, or by a combination of these methods, optionally at elevated temperature.
According to one embodiment, curing (4) can be performed by peroxidic crosslinking via radical hydrogen abstraction. In this reaction, a radical initiator is added that decomposes to form radicals. Each radical created directly or in a consecutive reaction can remove one hydrogen from the pre-crosslinked material, thereby becoming saturated. A radical site is simultaneously formed on a macromolecule of the pre-crosslinked material. Two macromolecular radicals formed in this manner can join to form a new Cxe2x80x94C bond. Multiple repetitions of this process on the pre-crosslinked material results in the final crosslinked material containing polyreaction products. The speed of this reaction is determined by the peroxide decomposition rate. Because such peroxidic crosslinking proceeds stoichiometrically and not as a chain reaction, the rate of final crosslinking can be controlled by the peroxide dosage. The amount of peroxide required depends on the desired end properties of the material containing polyreaction products, the type of peroxide, the form of delivery, and the type and quantity of the additional additives. Preferably, 0.05 to 10 wt % peroxide, in particular 0.5 to 10 wt %, relative to the weight of the binder, is used. Preferred peroxides include acyl peroxide, perketals, and aryl, alkyl, and aralkyl peroxides, or peroxides that release aroyl, phenyl, alkoxy, aralkoxy, or primary alkyl radicals.
Dicumyl peroxide, tert-butylcumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, di(tert-butyl)peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexyne(3), for example, are particularly preferred. In addition, crosslinking can be carried out with the addition of sulfur or silicon compounds singly or in combination with the peroxides listed above. The peroxide decomposition reaction can be induced thermally as well as by radiation, for example by UV radiation. This reaction is preferably thermally initiated. If the peroxides are already contained in the mixture, prior to the actual crosslinking the pre-crosslinked material should not be heated above a temperature at which little or no crosslinking is observed within the typical reaction time (so-called xe2x80x9cscorch temperaturexe2x80x9d).
According to a further embodiment, the curing reaction comprises a radical crosslinking of the free double bonds of the partially epoxidized carboxylic acid ester or of the double bonds of the crosslinking agent. In particular, organic peroxides commonly used as radical initiators or azobis compounds in customary forms of use can be used as radical-forming initiators or starters for curing (4). Examples of such include hydroperoxides such as cumene hydroperoxide and t-butylhydroperoxide, peroxyesters such as t-butylperoxybenzoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoctoate, and dimyristylperoxydicarbonate, peroxyketals such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane and 1,1-bis(t-butylperoxy)cyclohexane, dialkylperazides and diaralkylperoxides such as di-t-amyl peroxide, dicumyl peroxide, and 2,5-bis(t-butylperoxy)-2,5-dimethylhexane and -hexyne(3), and azobis compounds such as 2,2xe2x80x2-azobis(2-acetoxypropane) and 2,2xe2x80x2-azo-bis(2-methylpropionitrile). The radical chain reaction can be initiated thermally as well as by radiation, by UV radiation, for example.
The radical-forming initiator is preferably admixed with the other components in the form of a mixture with a mineral oil. Such a mineral oil acts as a wetting agent for the granulate and can simultaneously have a desensitizing effect.
The radical-forming initiator can optionally be compounded with the other components of the material in the compounding step (1) and/or before pre-crosslinking (2) and/or before molding of the flat article (3) in a second optional compounding step, or the radical-forming initiator can be incorporated by compounding before both crosslinking steps. Before shaping onto the surface of the appropriate material is performed, the radical-forming initiator, for example one of the aforementioned peroxides, can also be applied substantially to the surface by spraying, for example. Peroxides with different half lives and/or decomposition temperatures may optionally be added, so that, for example, decomposition of the peroxide required in the second crosslinking step (4) for curing does not occur during the first crosslinking step (2) of the method according to the invention.
Compounding (1) of the components is preferably carried out in an extruder or mixer. Furthermore, the method according to the invention may optionally include a second compounding step, such as the addition of peroxide, before molding of the flat article.
Surprisingly, the flat articles obtained by the method according to the invention are crosslinked throughout their entire cross section without further ripening, are non-tacky and flexible, and have a high bend restoring force; that is, they can be used directly after production. Hence, omission of the ripening process enables the method according to the invention to be carried out continuously.
The method according to the invention may optionally include an embossing step for the cured flat article, using the thermal transfer printing method, for example, known in the art.
The present invention further relates to a moldable, storable material that can be obtained through steps (1) and (2) of the method according to the invention.
This intermediate product has the composition described above.
The invention further relates to a flat article that can be obtained from the moldable, storable material according to the invention by molding and curing.
The flat articles produced by the method according to the invention are preferably used as floor or wall coverings. The flat articles can be present in a homogeneous form, or the pre-crosslinked material can be applied onto a substrate such as glass fiber mat, cardboard, jute fabric, or a substrate based on jute, such as mixtures of jute mat and polypropylene/polyester non-woven fabric.
The following example explains the present invention in more detail.

Method for producing flat articles from renewable raw materials